EP1634913B1 - Composition semi-conductrice à base de polymère - Google Patents

Composition semi-conductrice à base de polymère Download PDF

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Publication number
EP1634913B1
EP1634913B1 EP04021606A EP04021606A EP1634913B1 EP 1634913 B1 EP1634913 B1 EP 1634913B1 EP 04021606 A EP04021606 A EP 04021606A EP 04021606 A EP04021606 A EP 04021606A EP 1634913 B1 EP1634913 B1 EP 1634913B1
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EP
European Patent Office
Prior art keywords
polymer composition
copolymer
polymer
composition according
semiconductive
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EP04021606A
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German (de)
English (en)
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EP1634913A1 (fr
Inventor
Claes Broman
Lena Lindbom
Ulf Nilsson
Annika Smedberg
Alfred Campus
Roger Carlsson
Ola Fagrell
Jan-Ove BOSTRÖM
Anders Gustavsson
Andreas Farkas
Peter Carstensen
Anders Ericsson
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Borealis Technology Oy
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Borealis Technology Oy
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Priority to DE602004017458T priority Critical patent/DE602004017458D1/de
Application filed by Borealis Technology Oy filed Critical Borealis Technology Oy
Priority to AT04021606T priority patent/ATE412696T1/de
Priority to ES04021606T priority patent/ES2315603T3/es
Priority to EP08011794.8A priority patent/EP1978040B1/fr
Priority to EP04021606A priority patent/EP1634913B1/fr
Priority to CN200580030420.3A priority patent/CN101014653B/zh
Priority to CN200580030373.2A priority patent/CN101014652B/zh
Priority to KR1020077007860A priority patent/KR20070065362A/ko
Priority to PCT/EP2005/009720 priority patent/WO2006027261A1/fr
Priority to PCT/EP2005/009721 priority patent/WO2006027262A1/fr
Priority to CA2578002A priority patent/CA2578002C/fr
Priority to KR1020077005498A priority patent/KR100839947B1/ko
Priority to CA2578383A priority patent/CA2578383C/fr
Priority to US11/662,151 priority patent/US7732711B2/en
Priority to US11/574,942 priority patent/US8124877B2/en
Publication of EP1634913A1 publication Critical patent/EP1634913A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2958—Metal or metal compound in coating

Definitions

  • the invention relates to a carbon black semiconductive polymer composition, for use in power cables, with improved electrical performance and processability compared to other available semiconductive polymer compositions.
  • This invention relates also to a process for producing the polymer as well as the use of the polymer composition as a semiconductive layer of an electric AC-cable or DC-cable.
  • the metallic conductor is covered with an inner polymeric semiconductive layer, a polymeric insulation layer, an outer polymeric semiconductive layer, a metallic shield and finally a polymeric jacket.
  • a wide variety of polymeric materials have been utilized as electrical insulating and semiconductive shield materials for cables in numerous applications.
  • polymeric materials In order to be utilized in services or products, where a long-term performance is required, such polymeric materials, in addition to having suitable dielectric properties, must also be enduring and must substantially retain their initial properties for safe performance over many years of service.
  • a semiconductive polymer composition must fulfil a number of properties, of which the electrical properties are most vital.
  • Space charge performance of cables can be influenced by the selection of the components in the semiconductive material.
  • Space charge is an accumulation of electrical charges (electrons, holes and ions) inside the insulation leading to electrical field distortion. They emanate from components inside the insulation or from injection of electrons from the semiconductive layers.
  • Space charges trapped in high voltage insulation systems i.e. polymeric power cables
  • semiconductive polymer compositions which include an ethylene-acrylate copolymer, carbon black, stabiliser and organic peroxide crosslinking agent.
  • the molecular weight distribution which is the relation between the number of molecules in a polymer and the molecular weight of the individual molecules has to be considered.
  • the width of the distribution is given as a number defined as the ratio (Mw/Mn) between the "weight average molecular weight” M w divided by the "number average molecular weight” M n .
  • EP 1 065 672 A2 discloses a composition comprising an olefin polymer, such as a copolymer of ethylene and unsaturated esters with an ester content of at least about 5 % per weight based on the weight of the copolymer, and carbon black of about 25 % to about 45 % per weight based on the weight of the composition, with strictly defined properties, such as particle size of at least about 29 nm and a tint strength of less than about 100 %.
  • the application gives no information how the space charge properties can be influenced.
  • EP 0 644 558 A1 (Alcatel Cable) describes an insulative structure for cables, comprising at least one first semiconducting layer that is contiguous and coaxial with the core of the cable and is surrounded by a second electrically insulating layer which is itself covered by a third semiconducting layer, characterised in that the said semiconducting layers are exclusively composed of a matrix, comprising non-polar polymers whose components have a molecular weight (molar mass) greater than 1000.
  • CA 2145366 (BICC Cables Corp) discloses a semiconductive shield compositions containing a linear, single-site catalysed polymer formed by polymerising ethylene with at least one comonomer selected from C 3 to C 20 alpha-olefins; a carbon black selected from furnace carbon blacks that contain ash and sulphur in amounts of 50 ppm or less and have crystal dimensions L a and L c of 30 A or less, acetylene carbon blacks, and furnace carbon blacks having an ASTM grad of N-351; and a crosslinking agent.
  • the ethylene copolymer has a narrow molecular weight distribution due to the single-site catalyst and is therefore not multimodal.
  • the problem which has to be solved is to provide a semiconductive polymer composition with both improved space charge performance and good processability leading to long lifetime of the cables.
  • a semiconductive polymer composition comprising a non-polar multimodal ethylene homo- or copolymer produced in a polymerization process comprising a single-site catalyst; up to 10 wt% polar copolymer; and carbon black; wherein the polymer composition has a density of 870 to 930 kg/m 2 , a MFR 2 of 1 to 30 g/10 min. and a Mw/Mn of less than or equal to 10, which leads to a polymer composition with excellent properties, especially good space charge properties and good processability.
  • the density and the melt flow rate (MFR) are mainly affected by the type of polymer, but also by further additives.
  • MFR 2 and the ratio of Mw/Mn are understood according to this invention, as values of the semiconductive polymer composition measured without additives, especially without carbon black additives.
  • the semiconductive polymer composition of the invention combines the benefits of the properties achieved by the single-site catalyst used in a polymerization process and by keeping the above-mentioned ranges of the density, the MFR 2 and the ratio of Mw/Mn.
  • composition can be obtained by blending or by an in-situ-process as described below. However, it is preferred that the composition is obtained by an in-situ-process, more preferred by an in-situ-process as described below.
  • modality of a polymer refers to the form of its molecular weight distribution (MWD) curve, i.e. the appearance of the graph of the polymer weight fraction as a function of its molecular weight.
  • MWD molecular weight distribution
  • the different polymer fraction produced in the different reactors will each have their own molecular weight distribution which may considerably differ from one another.
  • the molecular weight distribution curve of the resulting final polymer can be looked as the superposition of the molecular weight distribution curves of the polymer fractions which will, accordingly, show two or more distinct maxima or at least distinctly broadened compared to the curves for the individual fractions.
  • a polymer showing such a polymer weight distribution curve is called bimodal or multimodal, respectively. Bimodal and multimodal polymers can be produced according to several processes e.g. as those described in WO 92/12182 .
  • the bimodal or multimodal polymer may be produced through polymerisation in a single reactor with the aid of a dual site coordination catalyst or a blend of different coordination catalysts.
  • the dual site catalyst may comprise two or more different single-site species each of which produces a narrow molecular weight distribution and a narrow comonomer distribution.
  • the inventive semiconductive polymer composition proves compared to unimodal material the better processability in terms of lower pressure during extrusion and longer time for scorch formation as demonstrated in the Brabender test (test method described below).
  • the multimodal ethylene homo- or copolymer is preferably produced in a multi-stage process in a multi-step reaction sequence such as described in WO 92/12182 (Borstar process).
  • ethylene is polymerized in a loop reactor in the liquid phase of an inert low boiling hydrocarbon medium. Then, the reaction mixture after polymerization is discharged from the loop reactor and at least a substantial part of the inert hydrocarbon is separated from the polymer.
  • the polymer is then transferred to a second or further step to one or more gas phase reactors, where the polymerization is continued in the presence of a gaseous ethylene.
  • the multimodal polymer produced according to this process has a superior homogeneity with respect to the distribution of the different polymer fractions which cannot be obtained, e.g. by a polymer mix.
  • the catalyst as above stated of the production of the polymer for the semiconductive polymer composition comprises a single-site catalyst, such as e.g. a metallocene catalyst.
  • a single-site catalyst such as e.g. a metallocene catalyst.
  • Preferred single-site catalysts are described in EP 688794 , EP 949274 , WO 95/12622 and WO 00/34341 . The contents of these documents are included herein by reference. However, the single-site catalyst is not limited to the catalyst as referred above.
  • the benefit of using a single-site catalyst in a multimodal process as described above is to achieve a peroxide crosslinkable semiconductive polymer making it possible to achieve sufficient crosslinking degree of the final product without formation of "scorch" during the extrusion.
  • crosslinking or precuring within the extruder causes gelation and adhesion of the polymer gel to surfaces of the equipment, with consequent risk of plugging.
  • the extruder therefore, has to be cleaned to remove adhering polymer gel and for every cleaning operation the equipment must be shut down, which entails a loss in production.
  • any gel lumps which do not clogg the production equipment can be incorporated into the product in the form of unwanted agglomerates. These defects might have major negative impact on the electrical performance of the cable.
  • the use of a single-site catalyst provides an uniform distribution of comonomer in the polymer chain.
  • the single-site catalyst in a multimodal process additionally comprises the advantage of a broader molecular weight distribution which leads to a better extrudability.
  • the inventive composition is extrudable at a temperature of less than 120°C, more preferred of less than 110°C, most preferred of less than 100°C.
  • the molecular weight of the multimodal ethylene homo- or copolymer can be characterized by the way of its melt flow rate (MFR) according to ISO 1133 at 190°C.
  • MFR melt flow rate
  • the melt flow rate is mainly depending on the average molecular weight. This is because long molecules give the material a lower flow tendency than short molecules.
  • An increase in molecular weight means a decrease in the MFR-value. It is required that the MFR 2 of the polymer composition is in the range of 1 to 30 g/10min., preferably of 2 to 25 g/10 min., and most preferred of 3 to 20 g/10 min..
  • the molecular weight distribution which is the relation between the number of molecules in a polymer and the molecular weight of the individual molecules has to be considered.
  • the width of the distribution given as a number defined as the ratio (Mw/Mn) between the "weight average molecular weight” M w divided by the "number average molecular weight” M n has to be less than or equal to 10, preferred less than or equal to 8, more preferred less than or equal to 7, and most preferred less than or equal to 6.
  • the composition has a Mw/Mn ratio of greater than or equal to 2.0, more preferred 2.5, still more preferred 3.0 and most preferred 3.5.
  • the Mw/Mn ratio ranges from 2.5 to 10, more preferably from 3 to 8 and most preferably from 3.5 to 6.
  • the Size Exclusion Chromatography SEC
  • GPC Gel Permeation Chromatography
  • the density of the polymer composition has to be in a given range.
  • the density has influence on the properties of the semiconductive polymer composition such as mechanical strength and shrinkage characteristics. Additionally, the optimum dispersion of possible additives is dependent on the right choice of the density. For this reason, a balance between these properties has to be established.
  • the density has to range between 870 to 930 kg/m 3 , preferably 880 to 915 kg/m 3 , more preferably 885 to 915 kg/m 3 .
  • the semiconductive polymer composition fulfils the above stated requirements of MFR 2 , Mw/Mn ratio and density, but also the multimodal ethylene homo- or copolymer produced in a polymersation process comprising a single-side catalyst.
  • the multimodal ethylene homo- or copolymer is non-polar as this leads to further improved space charge performance as for example shown in examples C vs B.
  • a non-polar homo or copolymer according to this invention is a polymer which has no permanent electric dipole moment originating from the monomers. Therefore, it is preferred that the polymer does not comprise polar groups, more preferred only consists of C and H and still more preferred the polymer is an saturated polymer consisting of C and H, only.
  • the multimodal ethylene homo- or copolymer comprises preferably a low molecular weight (LMW) ethylene homo- or copolymer fraction and a high molecular weight (HMW) ethylene homo- or copolymer fraction.
  • LMW low molecular weight
  • HMW high molecular weight
  • the LMW and/or HMW fraction may comprise only one fraction each or two or more subfractions.
  • ethylene homopolymer refers to a polyethylene that consists substantially, i.e. of at least 97 % by weight, preferably at least 99 % by weight, and more preferably at least 99.5 % by weight, and most preferably at least 99.8 % by weight of ethylene.
  • the multimodal ethylene homo- or copolymer is a bimodal polymer, more preferably a multimodal ethylene homo- or copolymer is a bimodal polymer consisting of one LMW fraction and one HMW fraction.
  • the copolymer comprises at least one C 3 -C 8 alpha-olefin as a comonomer, preferably at least one comonomer is selected from the group consisting of propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
  • the amount of comonomers in the ethylene polymer is 0.02 to 5.0 mol%, more preferably 0.05 to 2.0 mol%.
  • the multimodal ethylene homo- or copolymer is produced according to the below-described process.
  • the LMW fraction is produced in a loop reactor and the HMW fraction in a gas phase reactor.
  • a drawback with semiconductive materials based on non-polar polymers instead of EBA, EVA and other polar polymers is reduced adhesion between the inner semiconductive layer and the metal conductor leading to higher shrinkback and thereby possibly problems during cable installation.
  • the polymer composition comprises additionally a low level of carbon black and a polar copolymer, and optionally also other additives.
  • a polar copolymer is a compound which contains a polar covalent bond having a permanent electric dipole moment. Therefore, it is preferred that the copolymer comprises additionally elements others than C and H, still more preferred the copolymer comprises at least one element selected from the group consisting of O, S, P, Si and N.
  • the polymer comprises at least one element as defined above and/or at least one unsaturated bond.
  • the addition of polar copolymers in the composition will have a negative impact on the space charge performance showed by increased field enhancement factor (FEF) as defined in the description of the used test methods. It is, therefore, the polar copolymer is present in the total composition up to 10 wt%, preferred up to 8 wt%, more preferred up to 6 wt% and most preferred up to 5 wt% (corresponding to 0,7 wt% polar comonomer in semiconductive composition of example F - table I).
  • the small amount of polar copolymers in the semiconductive polymer composition has only a minor effect to the space charges, but a high bonus effect in respect of better adhesion, and processability.
  • the polar component is a high pressure copolymer. It is further preferred that the high pressure copolymer contains not more than 30 wt%, more preferably not more than 25 wt%, and most preferred not more than 20 wt% of polar comonomers. Furthermore, it is preferred that the high pressure copolymer, contains 5 to 30 wt%, more preferred 10 to 25 wt%, and most preferred 10 to 20 wt% of polar comonomer.
  • the high pressure polymer according to this invention is produced by radical polymerisation at pressures exceeding 1500 bar.
  • the high pressure polymer is preferably selected from the group consisting of ethylene-butyl-acrylate copolymer, ethylene-ethyl-acrylate copolymer, ethylene-methyl-acrylate copolymer, ethylene-vinyl-acetate copolymer or alternatively an ethylene-vinyl-silane copolymer.
  • VISICOTM vinyl-silane copolymer
  • VISICOTM vinyl-silane copolymer
  • a preferred vinyl-silane copolymer has a density of 923 kg/m 3 and a MFR 2 of 0.9g/10min.
  • the polymer is preferably selected from the group consisting of 1 to 3 wt% ethylene-vinyl-silane copolymer, most preferably 2 wt% ethylene-vinyl-silane copolymer, that is to say a copolymer containing 98 wt% ethylene and 2 wt% vinyl-silane.
  • the semiconductive polymer composition comprises conductive additives.
  • the dispersion of conductive additive, like carbon black, in the component is a critical requirement.
  • a poor carbon black dispersion or presence of foreign particles can cause negative impact on electrical properties.
  • carbon blacks containing ash in an amount of 100 ppm or less, and sulphur in an amount of 100 ppm or less. More preferably acetylene carbon black is used, because it gives not only a better surface smoothness, but also better space charge properties compared to furnace black.
  • the amount of carbon black is preferably less than or equal to 40 wt% of the total polymer, more preferably less than or equal to 35 wt% of the total polymer and most preferably less or equal to 30 wt% of the total polymer. More preferably the amount of carbon black ranges between 10 to 35 wt%, still more preferably 15 to 35 wt%.
  • composition is at least partially crosslinked.
  • a crosslinking agent is present during the extrusion.
  • Crosslinking agents such as organic peroxides
  • Particulary favourite peroxides include bis-(tert-butylperoxy-isopropyl)-benzene, dicumyl-peroxide and 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexane.
  • antioxidants may include polymerized 1,2-dihydro-2,2,4-trimethylquinoline or octadecyl-3,5-di-terz-butyl-4-hydroxy-hydrocinamat in amounts of preferably 0.1 to 2.5 wt%, more preferably 0.4 to 0.8 wt%, as preferred antioxidants.
  • suitable conventional antioxidants include sterically hindered phenols, phosphates and selected amines.
  • processing aids are not necessary to achieve a homogeneous semiconductive polymer composition, scorch retardants, polysiloxanes, polyethylene glycols (molecular weight from 10,000 to 30,000) and possibly other additives (preferably free from ionic species) may be incorporated into the semiconductive polymer composition to further improve the properties.
  • Processing aids, when present, are preferably used in amounts of 0.2 to 4.0 wt% based on the total weight of the semiconductive polymer composition.
  • the invention comprises also the process for producing the semiconductive composition, in particular the process for producing the multimodal ethylene homo- or copolymer in the semiconductive polymer composition.
  • the multimodal ethylene homo- or copolymer can be produced by blending but is preferred that the multimodal ethylene homo- or copolymer is produced in a multi-stage process like those disclosed in EP-B-0 517 868 and WO-A-96/18662 .
  • a first fraction is produced in one stage of a multi-stage polymerization process and a second fraction, preferably a high molecular weight copolymer fraction, preferably in another stage of the process. It is preferred that the second fraction, more preferably the high molecular weight fraction, is produced in the presence of a single-site catalyst. More preferably, the first fraction, still more preferably the low molecular weight copolymer fraction, is produced in a continuously operating loop reactor, where ethylene is polymerized in the presence of a polymerization catalyst as stated above and a chain transfer agent such as hydrogen.
  • the diluent is an inert aliphatic hydrocarbon, preferably isobutane or propane.
  • C 3 -C 8 alpha-olefin comonomer(s) is preferably added to control the density of low molecular weight polymer fraction.
  • the hydrogen concentration is selected so that the low molecular weight copolymer fraction has the desired melt flow rate. More preferably, the molar ratio of hydrogen to ethylene is between 0.1 and 1.0 mol/mol, most preferably between 0.2 and 0.8 mol/mol.
  • the target density of the low molecular weight copolymer fraction exceeds 955 kg/m 3
  • a preferred range of temperature is then from 90 to 110°C and the range of pressure is from 50 to 80 bar.
  • the slurry is intermittently or continuously removed from the loop reactor and tranferred to a separation unit, where hydrocarbons including not reacted C 3 -C 8 alpha-olefin comonomer(s) and especially the chain transfer agent are separated from the polymer.
  • the polymer containing the active catalyst is introduced into the gas phase reactor, where the polymerization proceeds in the presence of additional silane and/or functional C 3 -C 8 alpha-olefin comonomer(s) and optionally chain transfer agent to produce the high molecular weight copolymer fraction.
  • the polymer is intermittently or continuously withdrawn from the gas phase reactor and the remaining hydrocarbons are separated from the polymer.
  • the polymer is collected from the gas phase reactor and is at least a bimodal ethylene homo- or copolymer.
  • Conditions in the gas phase reactor are selected in a way that the ethylene homo- or copolymer has the desired properties.
  • the temperature in the reactor is between 70 and 110°C and the pressure is between 10 to 40 bar.
  • the hydrogen to ethylene molar ratio ranges from preferably 0.0001 to 0.02 mol/mol, more preferably 0.001 to 0.1 mol/mol, and the alpha-olefin comonomer to ethylene molar ratio ranges preferably from 0.03 to 0.7 mol/mol, more preferably from 0.04 to 0.6 mol/mol, and most preferably from 0.05 to 0.5 mol/mol.
  • the multimodal ethylene homo- or copolymer is mixed with the conductive additives, like carbon black, and preferably high-pressure polar polymers in the amounts as stated above.
  • this semiconductive polymer composition When producing this semiconductive polymer composition, the ingredients thereof, such as a multimodal ethylene homo- or copolymer, carbon black, high-pressure polymers and optionally additives should be mixed intimately in order to obtain a composition as homogeneous as possible.
  • the invention comprises also the use of a semiconductive polymer composition as described above as semiconductive layers of an electric AC-cable or of an electric DC-cable.
  • the invention comprises also an insulated electric AC-cable or DC-cable comprising a conductor, an insulating layer and semiconductive layers comprising the inventive semiconductive polymer composition, preferably consisting of the inventive semiconductive polymer composition.
  • the insulted electric DC-cable or AC-cable comprises a conductor, an inner semiconductive layer, an insulating layer and an outer semiconductive layer whereby at least one of the two semiconductive layers comprises a semiconductive polymer composition as described above.
  • the insulating layer of the AC-cable or DC-cable comprises, preferably is, a multimodal ethylene polymer produced in a multi-stage polymerisation process comprising a single-site catalyst.
  • the volume resistivity of the semiconductive materials is measured on crosslinked polyethylene cables with according to ISO 3915 (1981).
  • the construction of the cables is 50 mm 2 stranded Al-conductor and 5,5 mm thick insulation.
  • the inner and outer semiconductive layers have a thickness of 0,9 and 0,8 mm, respectively.
  • the cable line is a 1+2 system, thus one extrusion head for the inner semicon (semicon is used as an abbreviation for a semidonductive layer in a cable), and another for the insulation + outer semicon.
  • Specimens of length 13,5 cm are conditioned at 1 atm and 60 ⁇ 2°C for 5 ⁇ 0.5 hours before measurement.
  • the resistance of the outer semicon is measured using a four-terminal system using metal wires pressed against the semiconductive layer.
  • To measure the resistance of the inner semicon is it necessary to cut the cable in two halves, removing the metallic conductor.
  • the resistance between conductive silver paste applied on the specimen ends are then used to determine the volume resistivity of the inner semicon.
  • the space charge measurements were performed mainly with pressmoulded plaques with semiconductive electrodes on both sides.
  • the insulating part had a thickness of 2 mm and a diameter of 210 mm.
  • the corresponding dimensions for the semiconductive electrodes were 1 mm and 50 mm.
  • the plates were produced in a two-step process. First the insulation was pressmoulded from an extruded tape at 130°C for 10 min. The (pre-pressed) semiconductive electrodes were then pressed against the insulation in a second operation carried out at 180°C for 15 min to ensure crosslinking (if peroxide is present). Cooling to room temperature was done under pressure at a cooling rate of about 20°C/min. Mylar® film have been used as backing during the moulding.
  • the data in this document refer to non-degassed specimens (see Figure 1 ).
  • power cables of the same construction are those used for volume resistivity measurements have also been used as specimens for space charge measurements.
  • the space charge profiles after DC voltage application were determined by a pulse electroacoustic system (PEA). +2.5 kV (+3,5 kV for cables) 50 ns long pulses were used to excite pressure waves that were detected by a 52 mm thick piezo-electric PVDF film on the outer semicon. The signals were recorded at a rate of 0.25 GSamples/s and averaged 256 times in a digital oscilloscope. The charge distribution, i.e. the space charge density vs distance, can then be calculated.
  • PEA pulse electroacoustic system
  • FEF Field Enhancement Factor
  • the normal procedure for plaque tests is to subject the specimen to a high voltage DC voltage of +40 kV for three hours at 50°C, perform a measurement, then turn off the +40 kV source, short-circuit the specimen and then perform an additional measurement.
  • the first measurement is called a "voltage-on” test
  • the second test is a "voltage-off” test.
  • the applied voltage of the 5,5 mm cables is 100 kV DC.
  • Figure 2 shows an example of a voltage-on profile where the signal voltage data have been re-calculated to give the field enhancement factor at the cathode.
  • the leftmost sharp negative peak (at 0 mm) represents the negative charge on the cathode, i.e. the outer semicon, while the positive peak at 5,0 mm represents the charges on the anode, i.e. the inner semicon.
  • These peaks are present even if there is no space charge inside the insulation.
  • the charges between these two peaks are the charges inside the insulation, the space charges.
  • a flat horizontal profile between the electrode peaks means no space charges, but in this case positive charges are observed close to the outer semicon to the left. These are the charges causing the field enhancement.
  • the target is a flat horizontal line between the electrode peaks, meaning no space charges. In this case, FEF is close to 1,00.
  • the resistance to scorch (pre-crosslinking) at normal cable extrusion temperature is determined by the use of a Brabender kneader.
  • the kneader is heated to 125° and a plot of the kneader torque vs time is obtained. In the beginning the torque will decrease due to melting of the material, but then it will increased due to crosslinking.
  • the residence time is the time from the minimum to the time when the torque has increased with 1 Nm compared to the minimum value.
  • the shrinkback properties of the cables are measured according to AEIC CS5-94, specifying thermal cycling of cable specimen between ambient temperature and 50°C (2 hours at each temperature). The reported value is the shrinkage after one cycle only. Table I. Examples. Unit A B C D E F G Commercial EBA-based semicon with furnace black Commercial EBA-based semicon with acetylene black Single-site unimodal resin Single-site bimodal resin Single-site bimodal resin Single-site bimodal resin + polar copolymer Single-site Bimodal resin from Borstar process What's new from column to the left?
  • Furnace ⁇ acetylene black EBA ⁇ Single-site Unimodal ⁇ bimodal Reduced CB content Polar copolymer Borstar process EBA w% 60,2 63,35 5,00 5,00 Polymer 1 w% 64,35 Polymer 2 w% 25,6 26,60 24,54 Polymer 3 w% 37,75 39,75 36,81 Polymer 4 w% 68,35 TMQ antioxidant w% 0,80 0,65 0,65 0,65 0,89 1,03 0,65 Furnace black w% 39,0 Acetylene black w% 36,0 34,4 35,3 33,0 33,0 26,0 Bis(tert.butylperoxy isopropyl)benzene w% +1,00 +1,00 +1,00 +0,90 +0,90 +1,00 Volume resistivity - Inner semicon ⁇ -cm 125 2290 1830 1810 6865 Volume resistivity - Outer semicon ⁇ -cm 33 67 312 167 762 Space charge performance
  • Grade Polymer-type Modality Density (kg/m 3 ) Melt flow rate MFR 2 (g/10min) Polymer 1 Nonpolar Polymer Unimodal 902 10 Polymer 2 Nonpolar ethylene-octene copolymer Unimodal 897 1,6 Polymer 3 Nonpolar ethylene-octene copolymer Unimodal 885 30,0 Polymer 4 Nonpolar ethylene-buten-copolymer (Borstar technology) Bimodal 912 2.6
  • Example A and B demonstrate that improved space charge properties are obtained with acetylene black compared to furnace black.
  • a comparison between examples B and C shows that the replacement of the polar EBA base resin with a non-polar single site resin improve space charge properties as evidenced from the reduction of FEF from 1,23 to 0,93.
  • the processing properties are improved as shown by an increase of the Brabender residence time (measure of the scorch performance) from 160 to 264 minutes and by a reduction of the pressure in the extruder. Further improved processing properties can be achieved by reducing the amount of carbon black (example E).
  • the shrinkback properties are improved by adding 5% of a polar copolymer (example F) without any noticeable negative effect on the space charge behaviour.
  • Example G shows that possibility to use a bimodal resin from the Borstar process.

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Claims (21)

  1. Composition de polymère semi-conducteur comprenant :
    un homo- ou copolymère d'éthylène multimodal, produit dans un procédé de polymérisation comprenant un catalyseur à un seul site ;
    jusqu'à 10 % en poids de copolymère polaire ; et
    du noir de carbone ;
    laquelle composition de polymère possède une masse volumique de 870 à 930 kg/m3, un MFR2 de 1 à 30 g/10 min et un Mw/Mn inférieur ou égal à 10, les domaines indiqués étant mesurés sans additifs.
  2. Composition de polymère selon la revendication 1, laquelle composition possède un Mw/Mn supérieur ou égal à 2,0.
  3. Composition de polymère selon la revendication 1 ou la revendication 2, dans laquelle l'homo- ou le copolymère d'éthylène multimodal est un homo- ou copolymère d'éthylène bimodal.
  4. Composition de polymère selon l'une quelconque des revendications précédentes, dans laquelle le copolymère comprend au moins une alpha-oléfine en C3-C8.
  5. Composition de polymère selon la revendication 1, dans laquelle le copolymère polaire est un copolymère haute pression.
  6. Composition de polymère selon la revendication 5, dans laquelle le polymère haute pression est choisi dans le groupe constitué par l'éthylène-acrylate de butyle, l'éthylène-acrylate d'éthyle et l'éthylène-acrylate de méthyle, l'éthylène-acrylate de vinyle.
  7. Composition de polymère selon la revendication 5, dans lequel le copolymère polaire contient 5 - 30 % en poids de comonomères polaires.
  8. Composition de polymère selon la revendication 5, dans laquelle le copolymère est un copolymère vinyle-silane.
  9. Composition de polymère selon la revendication 1, dans laquelle le noir de carbone est du noir d'acétylène.
  10. Composition de polymère selon la revendication 1 ou la revendication 9, dans laquelle le noir de carbone est présent dans une proportion inférieure ou égale à 40 % en poids de la composition totale.
  11. Composition de polymère selon la revendication 10, dans laquelle le noir de carbone est présent dans une proportion de 10 - 35 % en poids de la composition totale.
  12. Composition de polymère selon l'une quelconque des revendications précédentes, dans laquelle la composition est partiellement réticulée.
  13. Composition de polymère selon l'une quelconque des revendications précédentes, dans laquelle la composition de polymère est extrudable à une température inférieure à 120 °C.
  14. Procédé de production d'un polymère selon l'une quelconque des revendications 1 à 13, dans lequel, dans une première phase d'une polymérisation à plusieurs phases de l'homo- ou du copolymère d'éthylène multimodal, la première fraction est produite, et dans une seconde phase une seconde fraction est produite en présence d'un catalyseur à un seul site.
  15. Procédé selon la revendication 14, dans lequel, dans la première phase, on utilise un réacteur à boucle, et dans la seconde phase on utilise un réacteur à phase gazeuse.
  16. Utilisation d'une composition de polymère selon l'une quelconque des revendications 1 à 13 comme couche de semi-conducteur dans un câble électrique pour courant continu.
  17. Utilisation d'une composition de polymère selon l'une quelconque des revendications 1 à 13 comme couche de semi-conducteur dans un câble électrique pour courant alternatif.
  18. Câble électrique isolé pour courant continu comprenant un conducteur, une couche intérieure de semi-conducteur, une couche isolante et une couche extérieure de semi-conducteur, moyennant quoi au moins une des deux couches de semi-conducteur comprend une composition selon l'une quelconque des revendications 1 à 13.
  19. Câble électrique isolé selon la revendication 18, dans lequel la couche isolante comprend un polymère d'éthylène multimodal produit dans un procédé comprenant un catalyseur à un seul site.
  20. Câble électrique isolé pour courant alternatif comprenant un conducteur, une couche intérieure de semi-conducteur, une couche isolante et une couche extérieure de semi-conducteur, moyennant quoi au moins une des deux couches de semi-conducteur comprend une composition selon l'une quelconque des revendications 1 à 13.
  21. Câble électrique isolé selon la revendication 20, dans lequel la couche isolante comprend un polymère d'éthylène multimodal produit dans un procédé comprenant un catalyseur à un seul site.
EP04021606A 2004-09-10 2004-09-10 Composition semi-conductrice à base de polymère Active EP1634913B1 (fr)

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AT04021606T ATE412696T1 (de) 2004-09-10 2004-09-10 Halbleitende polymerzusammensetzung
ES04021606T ES2315603T3 (es) 2004-09-10 2004-09-10 Composicion polimerica semiconductora.
EP08011794.8A EP1978040B1 (fr) 2004-09-10 2004-09-10 Composition polymère semi-conductrice
EP04021606A EP1634913B1 (fr) 2004-09-10 2004-09-10 Composition semi-conductrice à base de polymère
DE602004017458T DE602004017458D1 (de) 2004-09-10 2004-09-10 Halbleitende Polymerzusammensetzung
PCT/EP2005/009721 WO2006027262A1 (fr) 2004-09-10 2005-09-09 Composition polymere semi-conductrice
KR1020077007860A KR20070065362A (ko) 2004-09-10 2005-09-09 반도체성 중합체 조성물
PCT/EP2005/009720 WO2006027261A1 (fr) 2004-09-10 2005-09-09 Composition polymere semi-conductrice
CN200580030420.3A CN101014653B (zh) 2004-09-10 2005-09-09 半导体聚合物组合物
CA2578002A CA2578002C (fr) 2004-09-10 2005-09-09 Composition polymere semi-conductrice
KR1020077005498A KR100839947B1 (ko) 2004-09-10 2005-09-09 반도전성 고분자 조성물
CA2578383A CA2578383C (fr) 2004-09-10 2005-09-09 Composition polymere semi-conductrice
US11/662,151 US7732711B2 (en) 2004-09-10 2005-09-09 Semiconductive polymer composition
US11/574,942 US8124877B2 (en) 2004-09-10 2005-09-09 Semiconductive polymer composition
CN200580030373.2A CN101014652B (zh) 2004-09-10 2005-09-09 半导电聚合物组合物

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ES2315603T3 (es) 2009-04-01
CN101014653B (zh) 2013-10-30
CA2578383A1 (fr) 2006-03-16
KR100839947B1 (ko) 2008-06-19
ATE412696T1 (de) 2008-11-15
DE602004017458D1 (de) 2008-12-11
US20080190645A1 (en) 2008-08-14
KR20070051886A (ko) 2007-05-18
KR20070065362A (ko) 2007-06-22
CN101014652A (zh) 2007-08-08
US20080050588A1 (en) 2008-02-28
US8124877B2 (en) 2012-02-28
WO2006027261A1 (fr) 2006-03-16
CA2578002C (fr) 2011-04-19
CA2578002A1 (fr) 2006-03-16
CN101014653A (zh) 2007-08-08
CN101014652B (zh) 2010-12-01
EP1978040B1 (fr) 2015-06-17
CA2578383C (fr) 2010-05-25
EP1978040A1 (fr) 2008-10-08
WO2006027262A1 (fr) 2006-03-16
EP1634913A1 (fr) 2006-03-15

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